US20060284334A1 - Method for producing a shaped body from a polycondensate - Google Patents
Method for producing a shaped body from a polycondensate Download PDFInfo
- Publication number
- US20060284334A1 US20060284334A1 US10/569,249 US56924906A US2006284334A1 US 20060284334 A1 US20060284334 A1 US 20060284334A1 US 56924906 A US56924906 A US 56924906A US 2006284334 A1 US2006284334 A1 US 2006284334A1
- Authority
- US
- United States
- Prior art keywords
- polycondensate
- extruder
- melted
- melt
- molded part
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
- B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
- B29C48/83—Heating or cooling the cylinders
- B29C48/832—Heating
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- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- B29C2793/00—Shaping techniques involving a cutting or machining operation
- B29C2793/009—Shaping techniques involving a cutting or machining operation after shaping
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- B29C2948/92504—Controlled parameter
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- B29C2948/92819—Location or phase of control
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- B29C2948/92866—Inlet shaft or slot, e.g. passive hopper; Injector, e.g. injector nozzle on barrel
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/07—Flat, e.g. panels
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- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/251—Particles, powder or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/26—Scrap or recycled material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/001—Profiled members, e.g. beams, sections
- B29L2031/003—Profiled members, e.g. beams, sections having a profiled transverse cross-section
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
Definitions
- the invention relates to a method for manufacturing a molded part, in particular a profile, out of a polycondensate, in particular polyester, e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) or one of its copolymers, wherein the polycondensate is melted and later solidified again during the process.
- a polycondensate in particular polyester, e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) or one of its copolymers, wherein the polycondensate is melted and later solidified again during the process.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PET starting material is here derived directly from PET synthesis, or use is made of a recyclate, in particular a PET bottle recyclate (RPET), wherein work proceeds with the chips or flocks (flakes) obtained after washing and comminuting.
- RPET PET bottle recyclate
- these chips always contain slight quantities of water, wherein this water can involve residual water not yet expelled from the bottle washing process and/or water that newly penetrated the chips during their storage and transport.
- molded parts or profiles Finished products or semi-finished products that can be converted into finished products in processing steps like cutting, bending or thermoforming, are referred to as molded parts or profiles.
- the shape of the end product here corresponds to the shape of the molded part, or is directly derived from the shape of the molded part.
- the overall time for which the temperature of the polycondensate exceeds the melting point of the polycondensate during the process is preferably kept under about 30 seconds in the method according to the invention.
- PET Polyethylene terephthalate
- the polycondensate in its initial form, can be present as a loose material having an apparent density ranging from 200 kg/m 3 to 950 kg/m 3 , in particular in the form of granulate, powder, flocks or chips, wherein the latter typically consist of bottle recyclate (RPET).
- RPET bottle recyclate
- the method according to the invention is characterized by the fact that the overall time for which the polycondensate is present as a melt during the process consists of a first time segment in which the polycondensate still remains in the extruder after melted in the extruder, and a second time segment for which the still melted polycondensate is processed outside the extruder, wherein the first time segment preferably measures less than about 15 seconds.
- a retention time of the melt in the extruder of less than about 10 seconds is particularly advantageous.
- the additives are optimally mixed simultaneously by the kneading elements 13 during the melting process.
- the additives can also be incorporated after melting in the extruder.
- the additives are incorporated by means of a lateral loading device. Additional kneading or mixing elements can optionally be provided in the extruder, so that the additives are optimally mixed.
- the additives can also be added only after the extruder.
- Suitable additives include dyes and pigments, UV blockers, processing aids, stabilizers, impact modifiers, chemical and physical foaming agents, fillers like nucleating agents, particles that improve barrier or mechanical properties, reinforcing bodies, such as balls or fibers, along with reactive substances, for example oxygen absorbers, acetaldehyde absorbers or molecular weight-increasing substances, etc.
- the second time segment also involves the steps of molding and subsequently cooling to a temperature at which the reverse polycondensation reaction is essentially stopped.
- the molding step here typically takes place in a die, through which the polycondensate melt is extruded.
- Die outlets of varying shape can here be used. Simple shapes, such as round, annular or polygonal, in particular essentially rectangular, shapes are possible, as are complex shapes.
- An essentially rectangular profile comes about at a low width to height ratio (e.g., W:H ⁇ 10).
- a low width to height ratio is normally also present for the band-shaped, complex die outlets, giving rise to a profile.
- Such complex profiles have at least one partial surface arranged at an angle to another partial surface.
- the size of the molded part as measured in width and height results from the dimensions of the die outlet and possible re-molding steps, for example, stretching or constriction.
- At least the width or height of the die outlet, and in particular of the molded part normally exceeds 10 mm, especially 25 mm. In molded parts with a large width to height ratio, widths exceeding 100 mm, in particular 250 mm, are preferred. On the other hand, it is advantageous for at least one expansion of the molded part not to exceed 100 mm, in particular 50 mm, since the effect of cooling would vary too greatly between the outer wall and center of the molded part.
- the length of the molded part depends on how often the molded part is cut essentially transverse to the manufacturing direction. In this case, the length can exceed the width or height by several orders of magnitude, as with films or bands, for example. In profile rods, the length still clearly exceeds the length or width. By contrast, the length of the molded part can be less than or at least comparable to its width or height with respect to panes or blocks.
- the second time segment ends when all polycondensate has dropped below the melting point of the polycondensate T m . Rapid cooling is to take place for this purpose.
- Cooling can take place via a cooling medium, for example water or liquid nitrogen, or through contact with a cold surface, e.g., a cooling roll or a cooling jacket around the profile.
- a cooling medium for example water or liquid nitrogen
- FIG. 1 is the retention time of PET in a melted state permissible for an IV degradation from 0.81 to 0.76 as a function of the residual water content of a PET melt;
- FIG. 3 a - 3 d are examples for possible complex molded part or profile geometries.
- FIG. 2 a - 2 e show examples for possible simple molded part or profile geometries.
- FIG. 2 a shows a molded part or profile with rectangular cross section, wherein the W:H ratio is large, e.g., >10. This is known as a band profile.
- FIG. 2 b shows a molded part or profile with circular cross section. This is known as a round profile.
- FIG. 2 c shows a molded part or profile with annular cross section. This is known as a band profile.
- FIG. 2 d shows a molded part or profile with rectangular cross section, wherein the W:H ratio is small, e.g., about 1:1 to 3:1. This is known as a rod profile.
- FIG. 2 e shows a molded part or profile with rectangular cross section and with beveled edges. This is known as a strip profile.
- FIG. 3 a - 3 d show examples for possible complex molded part or profile geometries, wherein FIG. 3 a is a cross profile, FIG. 3 b a dovetail profile, FIG. 3 c an angular profile and FIG. 3 d a U profile.
- the method according to the invention makes it possible to also manufacture films or bands instead of molded pats or profiles.
- the films here preferably have a density of about 200 ⁇ m, and are in particular used as flexible packing films.
- the bands manufactured according to the invention preferably have a thickness of more than 200 ⁇ m, but can also be over 800 ⁇ m thick. The maximum thickness of these bands lies at roughly 5 mm. They are used in particular as rigid or semi-rigid packings.
- a polyethylene terephthalate granulate manufactured with an antimony catalyst, an initially intrinsic viscosity of 0.84 dl/g and a moisture content of 600 ppm was melted and degassed in a 30 mm ring extruder, and subsequently removed through a profile die by means of a gear pump. The profile was cooled directly after the die outlet. Panes with a diameter of approx. 40 mm and a thickness of approx. 5 mm were fabricated from the profile. The throughput measured 200 kg/h. The retention time in the melted state in the extruder measured approx. 4 seconds, and the retention time in the melted state after the extruder measured approx. 12 seconds.
- the manufactured panes had an intrinsic viscosity ranging from 0.79 to 0.80 dl/g, and an acetaldehyde content ranging from 1.5 to 1.8 ppm.
- a polyethylene terephthalate granulate manufactured with a germanium catalyst, an initially intrinsic viscosity of 0.75 dl/g and a moisture content of 2000 ppm was melted and degassed in a 30 mm ring extruder, and subsequently removed through a profile die by means of a gear pump.
- the profile was cooled directly after the die outlet.
- Panes with a diameter of approx. 40 mm and a thickness of approx. 5 mm were fabricated from the profile.
- the throughput measured 200 kg/h.
- the retention time in the melted state in the extruder measured approx. 4 seconds, and the retention time in the melted state after the extruder measured approx. 12 seconds.
- the manufactured panes had an intrinsic viscosity ranging from 0.71 to 0.72 dl/g, and an acetaldehyde content ranging from 2.0 to 2.5 ppm.
- a polyethylene terephthalate granulate was processed as in Example 2.
- the throughput measured 250 kg/h.
- the retention time in the melted state in the extruder measured approx. 3 seconds, and the retention time in the melted state after the extruder measured approx. 10 seconds.
- the manufactured panes had an intrinsic viscosity in the 0.71 dl/g range.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10348425A DE10348425B4 (de) | 2003-10-14 | 2003-10-14 | Verfahren zur Herstellung eines Profils aus einem Polykondensat |
DE10348425.6 | 2003-10-14 | ||
PCT/CH2004/000621 WO2005035221A1 (fr) | 2003-10-14 | 2004-10-12 | Procede pour produire un corps moule a partir d'un polycondensat |
Publications (1)
Publication Number | Publication Date |
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US20060284334A1 true US20060284334A1 (en) | 2006-12-21 |
Family
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US10/569,249 Abandoned US20060284334A1 (en) | 2003-10-12 | 2004-10-12 | Method for producing a shaped body from a polycondensate |
Country Status (10)
Country | Link |
---|---|
US (1) | US20060284334A1 (fr) |
EP (1) | EP1673211B1 (fr) |
JP (1) | JP2007531642A (fr) |
CN (1) | CN1842406A (fr) |
AT (1) | ATE439965T1 (fr) |
DE (2) | DE10348425B4 (fr) |
ES (1) | ES2331362T3 (fr) |
MX (1) | MXPA06001309A (fr) |
PL (1) | PL1673211T3 (fr) |
WO (2) | WO2005035220A1 (fr) |
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CN102268175A (zh) * | 2011-05-28 | 2011-12-07 | 福建师范大学 | 双向拉伸聚对苯二甲酸乙二醇酯扭结膜回收料制备塑料板凳方法 |
US20170106566A1 (en) * | 2012-05-31 | 2017-04-20 | Mohawk Industries, Inc. | Systems and methods for manufacturing bulked continuous filament |
EP3220782A4 (fr) * | 2014-11-18 | 2018-04-04 | Mohawk Industries, Inc. | Systèmes et procédés de fabrication de filament continu en vrac |
FR3066135A1 (fr) * | 2017-12-22 | 2018-11-16 | Sidel Participations | Production de recipients avec recyclage par extrudeuse bivis |
US10232542B2 (en) | 2012-05-31 | 2019-03-19 | Mohawk Industries, Inc. | Methods for manufacturing bulked continuous filament |
US10239247B2 (en) | 2012-05-31 | 2019-03-26 | Mohawk Industries, Inc. | Methods for manufacturing bulked continuous filament |
US20190118413A1 (en) | 2012-05-31 | 2019-04-25 | Mohawk Industries, Inc. | Systems and methods for manufacturing bulked continuous filament from colored recycled pet |
US10487422B2 (en) | 2012-05-31 | 2019-11-26 | Aladdin Manufacturing Corporation | Methods for manufacturing bulked continuous filament from colored recycled pet |
US10538016B2 (en) | 2012-05-31 | 2020-01-21 | Aladdin Manufacturing Corporation | Methods for manufacturing bulked continuous carpet filament |
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US10751915B2 (en) | 2016-11-10 | 2020-08-25 | Aladdin Manufacturing Corporation | Polyethylene terephthalate coloring systems and methods |
US11045979B2 (en) | 2012-05-31 | 2021-06-29 | Aladdin Manufacturing Corporation | Methods for manufacturing bulked continuous filament from recycled PET |
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US11279071B2 (en) | 2017-03-03 | 2022-03-22 | Aladdin Manufacturing Corporation | Method of manufacturing bulked continuous carpet filament |
US11351747B2 (en) | 2017-01-30 | 2022-06-07 | Aladdin Manufacturing Corporation | Systems and methods for manufacturing bulked continuous filament from colored recycled PET |
US11465325B2 (en) | 2017-11-09 | 2022-10-11 | Vinventions Usa, Llc | Method for manufacturing a closure for a product-retaining container |
US11473216B2 (en) | 2017-09-15 | 2022-10-18 | Aladdin Manufacturing Corporation | Polyethylene terephthalate coloring systems and methods |
US11565853B2 (en) * | 2017-11-09 | 2023-01-31 | Vinventions Usa, Llc | Method for manufacturing a closure for a product-retaining container |
US11807729B2 (en) | 2021-04-14 | 2023-11-07 | Goex Corporation | Polyethylene terephthalate-polyethylene naphthalate copolymer extruded sheet suitable for medical device packaging |
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JP5625271B2 (ja) | 2008-07-29 | 2014-11-19 | 住友化学株式会社 | 高分子化合物及びそれを用いた発光素子 |
WO2017077904A1 (fr) | 2015-11-04 | 2017-05-11 | 住友化学株式会社 | Procédé de commande d'élément électroluminescent et dispositif électroluminescent |
WO2017221822A1 (fr) | 2016-06-24 | 2017-12-28 | 住友化学株式会社 | Élément électroluminescent |
US11588119B2 (en) | 2017-04-27 | 2023-02-21 | Sumitomo Chemical Company, Limited | Light emitting device |
WO2018198974A1 (fr) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | Élément électroluminescent |
JPWO2019065389A1 (ja) | 2017-09-29 | 2020-11-26 | 住友化学株式会社 | 発光素子 |
JP6545879B1 (ja) | 2018-10-10 | 2019-07-17 | 住友化学株式会社 | 発光素子用膜及びそれを用いた発光素子 |
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- 2004-10-12 EP EP04761961A patent/EP1673211B1/fr active Active
- 2004-10-12 MX MXPA06001309A patent/MXPA06001309A/es unknown
- 2004-10-12 AT AT04761961T patent/ATE439965T1/de not_active IP Right Cessation
- 2004-10-12 CN CNA2004800247780A patent/CN1842406A/zh active Pending
- 2004-10-12 JP JP2006521326A patent/JP2007531642A/ja active Pending
- 2004-10-12 DE DE502004009934T patent/DE502004009934D1/de active Active
- 2004-10-12 WO PCT/CH2004/000621 patent/WO2005035221A1/fr active Application Filing
- 2004-10-12 ES ES04761961T patent/ES2331362T3/es active Active
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US11242622B2 (en) | 2018-07-20 | 2022-02-08 | Aladdin Manufacturing Corporation | Bulked continuous carpet filament manufacturing from polytrimethylene terephthalate |
US11926930B2 (en) | 2018-07-20 | 2024-03-12 | Aladdin Manufacturing Corporation | Bulked continuous carpet filament manufacturing from polytrimethylene terephthalate |
US11807729B2 (en) | 2021-04-14 | 2023-11-07 | Goex Corporation | Polyethylene terephthalate-polyethylene naphthalate copolymer extruded sheet suitable for medical device packaging |
Also Published As
Publication number | Publication date |
---|---|
DE10348425A1 (de) | 2005-05-25 |
ES2331362T3 (es) | 2009-12-30 |
WO2005035220A1 (fr) | 2005-04-21 |
MXPA06001309A (es) | 2006-05-04 |
JP2007531642A (ja) | 2007-11-08 |
DE502004009934D1 (de) | 2009-10-01 |
PL1673211T3 (pl) | 2010-03-31 |
DE10348425B4 (de) | 2008-07-24 |
EP1673211B1 (fr) | 2009-08-19 |
EP1673211A1 (fr) | 2006-06-28 |
ATE439965T1 (de) | 2009-09-15 |
CN1842406A (zh) | 2006-10-04 |
WO2005035221A1 (fr) | 2005-04-21 |
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